Vat dyestuffs of the anthrapyridone and the anthrapyrimidone series



Patented Apr. 18, 1933 I UNITED "sq" ims o'r'i'o BAYER, OF EEANxEoEw oN rHE MAm, AND nrrz BAUMANE, or LEvEExUsEN- YORK, N. Y., A CORPORATION OF DELAWARE var DYESTUEFSROFJEEANTHRALPIRTDONEVAND THE ANTimArY nnpoNE SERIES Ro.Drawii\g.- Application. filed January 5,1931; Serial No. 506,832, ana mf eer'manirfiaiguar 15, 1930.

Dur'int'eaition relates to newtat corresponding. probably to the. general for: mula; a

or. N; manne- X' y wherein R means "CH drogen and {the other X the grouping no;

in which 7 the anthraq'uinone residue may contain. an aminogroupiinthe position signified by Y. Thepresenthew dyestufis are when dry yellow to bluish red crystalline substances, which are scarcelysoluble in organic solvents, and dye-the"vegetable fiber from areddish tobrownish vat yellow'to bluish red shades of an excellent fastness,

which shades are distinguished by'agreater deepening a ndiintensity than is shown by the Pr u t p p r d r m' an hr qu eicarboxylie acid halides and aminmanthra; quinolwsih .T ein i th e dye o l s v are ,s'olub1e inthe vat 'totlie usual degree is v .very surprising-in view of the presenoe of the; notivattable ipyri'done and pyri nidone f residue respectively.

1 The; new dye stufis 'ai ell obtainedi con densing ananthraquinonefl-earboxylic acid halide or a nuclear"substitution-product thereof containing an, a ninogroupvwith a N-alkylanthraPyridone or-anthrapyrimidone' derivative containing an" aminogroup 'attached'tothe- :or fi-position-ofi the anthrlaquinone nucleus. vThe).eondensatio'n re:

actionis advantageousfiz carried out in the presence of a suitable diluent such as nitrobenzene or trichlorobenzeiie.

When using as a componentof condensat Y mula are obtained by subsequent alkylation.

f In orderto further illustrate our'invem tion the followingexamples' "are given, the

parts being by weight and all temperatures in centigrade degrees, but it is, however, to

be understood, that our invention is not iim V ited to the particular; products norireactf ing conditions nientionedthereixn-ii E'mamplei f of 4 m n f-L9-(l methyl) as thr apyridone aremixdwith about800 parts of nitrobenzenef'the mixture -'is' heated at about-200 and then 50 parts of 'anthraquin one-2-carboxylic acid 'ohloride are added;

When the evolution of hydrochloric acid gas has ceased the "separated crystalline clondensation product is filtered vofl' and washed out with alcohol. -It'dyes cotton golden yel- The new low shadesof a: fastness.

correspond probably to the for dyestufi's mula I v oo 7 r J whenrplacing E mp thejimthrav'r Example 3 30 parts of 5-amino-1.9-(l-methyl)-anthrapyridone (which crystallizes from glacial acetic acid as orange red neddles, which melt above 300 and dissolve in sulfuric acid with a yellow orange color) are mixed with about 500 parts of technical o-dichlorobenzene and 30 parts of anthraquinone-2-carboxylic acid chloride and the mixture is heat ed to boiling'until the evolution of hydrochloric acid has ceased. Then the separated crystalline condensation product is filtered off at about 100 and washed out with alcohol. The new dyestufi dyes cotton-from a reddish brown vat greenish yellow shades and corresponds probably to the formula:

l. OEQO Example 4 When condensing 5 amino 1.9 (1' methyl) -anthrapyridone with l-aminoanthraquinone-2-carboxylic acid chloride in the manner described in the foregoing examples a new dyestufi is obtained which dyes cotton from a brownish red vat brick-red shades of parts of nitrobenzene.

a good fastness. The new dyestufi corresponds to the probable formula:

(|) NE: NH i Example 5 30 parts of 4-amino-N-methyl-1.9-anthrapyrimidone are introduced into about 500 The mixture is dehydrated by heating at 180 in an open vessel for some time. Then at about 120 34: parts of l-aminoanthraquinone-2-carboxylic acid chloride are added and the mixture is heated at 160-17 0 until no more starting material can be detected. Then the new dyestuff which separates in form of beautiful brownish crystals is filtered off at about120 and washed out with alcohol. It is scarcely soluble in organic solvents, soluble in concentrated sulfuric acid with a red color without fluorescence; by pouring the solution on water the dyestulf; is precipitated as bluish red flakes. The new dyestuif dyes cotton from a brownish red vat full clear bluish red shades of a good fastness. It corresponds to the probable formula:

/C(z\fi N III-CH3 II o The i-amino-N-methyl-1.9-anthrapyrimidone used for the condensation may be obtained by treating l-methylamino-l-benzoylamino-anthraquinone with urea and by subsequently splitting off the benzoyl-group according to U. S. Patent 928,891. The compound represents a substance crystallizing as bluish red needles. It dissolves in sulfuric acid with an orange red color and a yellow fluorescence, in pyridine with a bluish red color and a likewise yellow fluorescence.

Example 6 28 parts of anthraquinone-2-carboxylic acid are transformed into the chloride by heating it with the same quantity of thionylchloride with addition of about 500'parts of nitrobenzene. The excess of thionylchloride is removed by vdistillation in vacuo. Then at about 120 25 parts of 4-amino-L9-anthrapyrimidone are added and the mixture is heated at about 200 until the reaction is finished. The condensation product is filtered off at about 100. When dry it represents an orange brown compound soluble in sulfuric acid with a yellow brown color and strongly attacked by the action of an alkali.

By methylating it with p-toluene-sulfonic methylicester with addition of a sodium carbonate solution the orange red N-methyl-1.9-

anthrapyrimidone 4 -anthraquinone-fl-car boxylic acid amide is formed. It corresponds to the probable formula:

t and dyes cotton reddish orange shades.

Example 7 When replacing in the foregoing example v the 4-amino-N-methyl-L9-anthrapyrimidone by the isomeric 5-amino compound a dyestuif is formed, which dyes cotton from a red vat red shades and corresponds to the probable formula:

We claim 1., Vat dyestuffs corresponding probably to V the general formula: V vother X the grouping.

R means CH or N and one hydrogen andthe other X the grouping in which the anthraquinone radical may contain an aminogroup in the positionsignified by Y, which new dyestuffs are when dry 7 7 yellow to bluish red crystalline substances,

which are scarcely soluble in organic solvents,

wherein one X means hydrogen and the I to r in which the anthraquinone radical may contain an aminogroup in the position signified by Y, which new dyestufis are when dry yellow to bluish red crystalline substances,

whichare scarcely soluble in organic solvents.

and dyethe'vegetablefiber from a reddish to brownish vat yellow to bluish red shades of a good fastness. v

3. he vat dyestufi of the probable formu'laz. 11

o0 Hc N-om which dyestufi' dyes cotton from a reddish brown vat full red shades.

yellow to bl'uish red shades of. V

las

4;. The at dyestuffs of the probable forwherein one means hydrogen and the other X the grouping:

II IIIH in which the anthraquinone radical may contain an aminogroup in the position signified by Y, which new dyestufl's are when dry yelloW to bluish red crystalline substances, which are scarcely soluble in organic solvents and dye the vegetable fiber from a reddish to brownish Vat yellow to bluish red shades of a good fastness.

5. The Vat dyestuflf of the probable formula:

lfil NCHs NH NHzL which dyestuif dyes cotton from a brownish red Vat full clear bluish red shades. 

